Unsymmetrical diphenyl carbonates

ABSTRACT

BACTERICIDAL DETERGENT COMPOSITIONS CONTAINING AS ANTIBACTERIAL AGNETS, UNSYMMETRICAL DIPHENYL CARBONATES WHICH CONTAIN AS ONE ALCOHOL MOIETY A PHENOXYPHENYL RADICAL WHCH IS UNSUBSTITUTED OR SUBSTITUTED BY HALOGEN AND/OR LOWER ALKYL OR TRIFLUOROMETHYL, AND AS A SECOND ALCOHOL MOIETY A PHENYL RADICAL WHICH IS UNSBUSTITUTED OR BEARS CERTAIN SUBSTITUENTS.

United States Patent 01 ace 3,681,249 Patented Aug. 1, 1972 3 681 249 UNSYMMETRICAL blPllENYL CARBONATES Walter Traber, Riehen, and Anton G. Weiss, Basel, Switzerland, assignors to Ciba-Geigy Corporation, Ardsley,

No Drawing. Original application July 26, 1968, Ser. No. 747,795, now Patent No. 3,634,484. Divided and this application Jan. 14, 1971, Ser. No. 106,533

Int. Cl. Clld 3/48 US. Cl. 252-406 5 Claims ABSTRACT OF THE DISCLOSURE This is a division of application Ser. No. 747,795, filed July 26, 1968, now Pat. No. 3,634,484.

The present invention concerns new unsymmertical diphenyl carbonates, processes for the production thereof, the use of these new esters as active substances for the disinfection of laundered goods and in antibacterial agents and preparations for combatting bacteria as well as the material treated with these carbonic acid esters.

Halogenated 2-hydroxy-diphenyl ethers, having antibacterial properties, are described in British Pat. No. 1,024,022 and esters of halogenated 2-hydroxy-diphenyl ethers with aliphatic dicarboxylic acids, also having antibacterial properties, are disclosed in Belgian Pat. No. 659,636. These types of compounds, however, are only insufficiently suitable for the disinfection and protection of laundered goods, since their bactericidal activity is completely lost when used in washing liquors containing chlorine.

The new unsymmetrical 'diphenyl carbonates correspond to the general Formula -I In this formula R and R independently of each other each represent hydrogen or a halogen atom of an atomic number of at most 35,

the benzene ring B is unsubstituted or is monoto trisubstituted by halogen of an atomic number of at most 35 or by lower alkyl, or monoor disubstituted by the trifluoromethyl group,

the benzene ring C is unsubstituted or is monoor polysubstituted by halogen of an atomic number of at most 35, or monoto tri-substituted by alkyl or alkoxy with 1 to 9 carbon atoms, or monoor di-substituted by the trifluoromethyl group, or substituted by the phenyl or by a halogenated phenyl radical.

In the general Formula I, by halogen of an atomic number of at most 35, particularly chlorine and bromine are to be understood; and as a halogenated phenyl radical of the benzene ring C one monotri-substituted by chlorine and/ or bromine is meant. Lower alkyl substituents of the benzene ring B have 1 or 2 carbon atoms, i.e. they are the methyl or the ethyl radicals, whilst for the benzene ring C besides those alkyl groups with 1 to 9 carbon atoms, alkoxy radicals with preferably 1 to 3 carbon atoms, particularly the methoxy and ethoxy radical are meant.

The new carbonic acid diesters of general Formula I have good bactericidal and bacteriostatic properties against Gram-positive and Gram-negative bacteria such as Staphylococcus spec., Staphylococcus aareus Smith, Staphylococcus Jactis, also Bacillus mescentericus, Bacillus pumilus, Bacillus subtilis, coli forms, Corynebaclerium diphtheriae, Clostridum botu'lium, Cl stridium butyricum, Clostridium welchii, Clostridium tetani, Klebsiella pneumoniae, Alcaligenes faecalis, Sarcina spec., Salmonella pullorum, Salmonella typhi, Salmonella para typhi A and B, Salmonella typhi murium, Salmonella enteritidis, Shigella dysenteriae, Shigella fl xneri, Brucella ab 'rtus, Proteus mirabilis, Achromobacter spec., Serratia marcescens, Pasteurella pseud tubercul sis. In addition, they have low toxicity to warm blooded animals and have no irritant action at all on the skin and mucous membranes. Because of these good properties, the new esters can be used for the most various purposes, e.g. for the protection of organic materials and useful objects, particularly as bactericidal additives to cleansing materials of all types such as soaps and detergents.

Moreover, the new esters can serve as active substances in pharmaceutical preparations such as ointments, powders, distinfectants of all types, cosmetic and hygienic preparations, both for internal and external use.

The carbonic acid diesters according to the invention are obtained either by reacting a hydroxydiphenyl ether of the general Formula II wherein R and R have the meanings given above and the benzene ring B has the definition given in Formula I, with a chlorocarbonic acid ester of the general Formula III C -O(iJ-Cl i) (III) or with its components, namely phosgene and a phenol of the general Formula IV which are capable of forming in situ such a chlorocarbonic acid ester, in which formulae the benzene ring C can be substituted as given in Formula I, the reaction preferably being performed in the presence of an acid binding agent; or by reacting a hydroxydiphenyl ether of the general Formula II with phosgene to give a 2-phenoxyphenyl chlorocarbonate of the general Formula V V also belong to a known class of compounds which can be produced in the known way by reaction of a phenol with phosgene.

For the production of the new carbonic acid diesters of the general Formula I, the following hydroxydiphenyl ethers of the general Formula II, for example, can be used:

3',4-dichloro-2-hydroxy-diphenyl ether 3',4,4trichloro-Z-hydroxy-diphenyl ether 2,4'-dichloro-2-hydroxy-diphenyl ether 2',4'-dibromo-4-chloro-2-hydroxy-diphenyl ether 4-chloro-2-hydroxy-diphenyl ether 4,4-dichloro-2-hydroxy-diphenyl ether 4-ch10ro-4'-bromo-2-hydroxy-diphenyl ether '-methyl-4-chloro-2-hydroxy-diphenyl ether 4,4'-dichloro-5-bromo-Z-hydroxy-diphenyl ether 4,2',4'-trichloro-5-bromo-Z-hydroxy-diphenyl ether 4,2,4'-trichloro-2 hydroxy-diphenyl ether 4-bromo-4'-chloro-2-hydroxy-diphenyl ether 2,4,5,4-tetrachloro-Z-hydroxy-diphenyl ether 4,2',4'-tribromo-2-hydroxy-diphenyl ether 4-bromo-2', '-dichloro-Z-hydroxy-diphenyl ether 4,4'-dibromo-Z-hydroxy-diphenyl ether 4'-chloro-Z-hydroxy-diphenyl ether and 4,4'-dichloro-3'-trifluoromethyl-Z-hydroxy-diphenyl ether.

2-hydroxy-diphenyl ethers of Formula II are preferred which are substituted by at least one and at most 3 halogen atoms or by 1 to 2 halogen atoms and/or lower alkyl radicals and/ or trifluoromethyl radicals.

In the process according to the invention, organic bases such as tertiary amines, e.g. pyridine, triethylamine, and inorganic bases such as the hydroxides and carbonates of alkali and alkaline earth metals are used as acid binding agents. Halogenated hydrocarbons, amides, ethers and ether-type compounds are used as solvents or diluents in the process mentioned.

The production of some new carbonic acid diesters of the general Formula I is described in the following examples. The temperatures are given in degree centigrade and parts are to be understood as parts by weight and are related to parts by volume as grams to milliliters.

EXAMPLE 1 11.9 parts of 2',4',4-trichloro-2-hydroxy-diphenyl ether and 3.24 parts of pyridine are dissolved in 27 parts by volume of methylene chloride. 10.75 parts of chlorocarbonic acid-(4-n-nonylphenyl)-ester dissolved in 10 parts by volume are then added dropwise to this solution at a temperature of and 5, whereupon the reaction mixture is stirred for 2 hours at room temperature. The precipitate formed is filtered off and washed with methylene chloride. The methylene chloride filtrate is then washed several times with water and dried. After distilling off the methylene chloride, the O-[2- (2",4"-dichlorophenoxy)-5-chlorophenyl]-O-(4'-n-nonylphenyl) carbonate is distilled: B.P. 200210/ 0.005 torr.

EXAMPLE 2 (a) 210 parts of phosgene are sparged at 5 to into a solution of 435 parts of 4,2, '-trichloro-2-hydroxy-diphenyl ether in 900 parts by volume of dry toluene. At 0 to 5 a solution of 166 parts of triethylamine in 300 parts by volume of dry toluene is then added dropwise. The reaction mixture is stirred for 4 hours at room temperature, and the excess phosgene is then removed by sparging dry nitrogen into the mixture. The precipitated amine hydrochloride is filtered off and the filtrate evaporated in vacuo. The residue is vacuum-distilled and 2-(2,4'-dichlorophenoxy)-5-chlorophenyl chlorocarbonate is obtained, B.P. 160-162/0.05 torr.

(b) 80 parts of 4-phenyl-phenol are dissolved in 300 parts by volume of methylene chloride, 39.5 parts of pyridene are added and the solution cooled to 10. At a temperature of 10-15", 176 parts of 2-(2',4'-dichlorophenoxy)-5-chloropheny1 chlorocarbonate diluted with 200 parts by volume of methylene chloride are added dropwise. The reaction mixture is stirred at room temperature for two hours, filtered, and the filtrate washed with water and dried with magnesium sulfate. After evaporating the solvent the residue is recrystallised from isopropanol.

O-[2-(2",4"-dichlorophenoxy) 5 chlorophenyl]-O- (4' phenyl-phenyl) carbonate is thus obtained, M.P. 118- 120.

The new carbonic acid diesters of general Formula I given in the following table are obtained in the way described in the above examples.

Boiling point/(B.P.)

Compounds Melting point/(M.P.)

0-[2-(4-chlorophenoxy) -5-dicblorophenyl1- B.P. -205/0.0001 torr.

O-(4-n-octylphenyl) carbonate.

0'[2-(4-chlorophenoxy)-5-chlorophenyl]- B.P. 210/0.000l torr.

O-(4-n-nonylphenyl) carbonate.

O-[2-(2",4-dichlorophenoxy)-5-chloropheny1]- B.P. 200220/0.001 torr.

O-(4-n-octylphenyl) carbonate.

O-[2-(2,4-dichlorophenoxy)-5-c orophenylI- B.P. 205215/0.02 torr.

0-(4-tert-octylphenyl) carbonate.

O-[2-(4-chlorophenoxy)-5-chloropl1enyl]-O- B.P. 185l95/0.001 torr.

(4-tert.octylphenyl) carbonate.

0-[2-(2 4"-dichlorophenoxy)-5-ch101'o- M.P. l12113.

phenyll-O-(2',4-di-tert.butyhV-methylphenyl) carbonate.

O-[2-(2 ,4-dichlorophenoxy)-5-chlorophenyl1-0-(4-methoxyphenyl) carbonate.

O-[2-(4"-methylphenoxy)-5-bromophenyl]- O-(2'-chloro-4-phenyl-pheny1) carbonate.

0-[2-(2,4-diehlorophenoxy)-4-brorno-5- chlorophenyl1-O-(4-methoxyphenyl)- carbonate.

0-[2-(2,4-dichlorophenoxy)-4-bromo-5- ehlorophenyl]-O-(2,4-di-tert.butyl-5- methylhenyl) carbonate.

0-[2-(2,4 -dichloropbenoxy)-4-bromo-5- chlorophenylI-O-(2phenyl-phenyl) carbonate.

O-[2-(2 ,4-dibromophenoxy) -5-chlor0- phenyH-O-(4-methoxypheny1) carbonate.

O-[2-(2,4-dibromophenoxy)-5-chlorophenyl]-O-(2-phenyl-phenyl) carbonate.

B.P. 180200/0.001 torr.

B.P. 200-220/0.001 torr.

B.P. 180200/0.001 torr.

B.P. 200220/0.001 torr.

B.P. 189200/0.001torr.

B.P. 200220/0.001 torr.

B.P. 200220/0.001 torr.

B.P. 160180/0.001 torr.

M.P. l55-157.

B.P. 200220/0.001 torr.

B.P. 200220/0.001 torr.

The carbonic acid diesters of general Formula I have an excellent growth-inhibiting action in various series of tests, such as the incorporation test (testing of the growth of bacteria or fungi on culture medium into which various concentrations of the active substances have been incorporated) described by X. Biihlmann, W. A. Vischer and H. Bruhin [Zbl. Bakt. Abteilung I, Originale, 180, 327- 334 (1960)], and the diffusion test (measurement of the breadth of zones of inhibition) described by H. Bruhin and X. Biihlmann [Path. Micro-Biol. 26, 108-123 (1963)], against Gram-positive and Gram-negative bacteria such as Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Salmonella typhi.

Bacteriostatic activity in vitro (diiiusion test).The test substance is dissolved in a suitable solvent in a concentration of 5000 'y/ cc.

Sterile strips of filter paper x 85 mm., liquid takeup of each strip about 0.1 cc.) are dipped in the solution of test substance and then hung up to dry. Each strip is then placed in a petri dish (85 mm. inner diameter, filled with 20 cc. culture medium) and the dishes, containing uninoculated medium, are placed for 16 hours in an incubation chamber to allow the test substances to penetrate into the media. Only then is a strip of the medium inoculated with the bacteria for the test, after which they are bred for 24 hours at 37 C.

As result, the size of the zone of inhibition, including Bacteriostatic activity in vitro (incorporation test).- The active substance to be tested is dissolved in a suitable solvent and, if possible, the solution is further diluted with the same solvent. The concentrations of the solutions of active substance are so chosen that, after addition of the culture medium, the desired final concentration is attained. With water as solvent, the ratio of solution: culture medium should be about 1:10, with an organic solvent it is generally 1:100. In order to exclude a bacteriostatic action of the solvent used, a control is run with the solvent.

The solution of active substance is added to the still liquid agar culture and the mixture is poured into petri dishes so that each contains 20 cc. After it has solidified, the culture medium is inoculated with suitable suspensions of bacteria. The media are then placed in an incubation chamber for 24 hours at 37 C. The test is evaluated by determining the lowest concentration at which growth of the bacteria is completely inhibited.

The figures given in the following table are the minimal concentration which inhibits growth. They are shown in p.p.m. (parts of active substance per parts of diluent), which corresponds to an amount of 17 per cc.

The following tests were made to determine the bacteriostatic activity in washing liquors containing chlorine:

The active substance, previously dissolved in a ratio of 1:100 in dimethyl formamide, is added in the concentrations given to a washing liquor containing 2.5 g./ litre soap and 2 cc./litre of an aqueous sodium hypochlorite solution containing active chlorine (B).

Cotton fabric is introduced into this liquor (liquor ratio 1:20) and the liquor is heated to C. The textile is treated for 20 minutes at this temperature, then rinsed twice for 3 minutes at 40 C. with permutit-water (liquor ratio 1:20), wrung out and dried. Circular samples (20 mm. diameter) are cut from this washed and treated textile and laid on agar plates which have been inoculated previously with 24 hour old cultures of Staphylococcus aureus SG 511 or Escherichia coli 96. The agar plates are then put into an incubating chamber for 24 hours at 37 C.

The values summarised in the following table give the extent of the zones of inhibition around the sample in mm the sign means no formation of colonies and the sign means formation of colonies under the sample.

Staph.

Concenaureus E. colt tration Compounds in p.p.m. A B A B 0-[2- -chlorophenoxy)-5-chlorophenyl]-O-(4-n-octylphenyl) 10- 10- 10- 8- carbonate 200 10- 10- 11- 10- O-[2-(2",4-dichlorephenoxy)-5- phenyl) carbonate 200 7- 4- 2- 1- O-[2-(4-chl0rophenoxy)-5-ch1orophenyl]-O-(4-tert. octylphenyl) 100 8- 4- 9- 5- carbonate. 200 9- 6- 10- 6- O-[2-(2 ,4-dich1or0pnenoxy) -5- phenyl) carbonate 200 8- 7- 6- 5- O-[2-(2,4-dichlorophenoxy)-5- phenyl) carbonate L 200 7 6- 5- 5- O-[2-2 ,4-dichlorophenoxy) -5- chlorophenyll-O -(4-methoxy- 100 12- 9- 6- 3- phenyl) carbonate 200 14- 14 6- 5- 2-hyldroxy-4A -drchlorophanyl 12- e er 2-hyl tliroxy-4,2,4-trichlorophenyl lget er Di[2-(4-chlorophenoxy)-5-chloro- 100 11- 0+ 12- 0+ phenyl] oxalate 1 200 13- 0+ 12- 0+ D1-[2-(2 ,4 -drchlorophenoxy) -5- 100 lO- 0+ 9 0+ chlorophenyl] oxalate 1 200 12- 0+ 10-- 0+ 1 Compounds known from British Patent No. 1,024,022 and Belgian Patent No. 659,636.

This stability of action of the carbonic acid diesters according to the invention is maintained not only in washing liquors containing hypochlorite but also generally in all washing or rinsing liquors which contain active chlorine.

As wash-active substances, washing or rinsing liquors can contain, e.g. anion active compounds such as aromatic sulphonic acids substituted by lipophilic groups or their water soluble salts such as the sodium salt of dodecylbenzene sulphonic acid, or water soluble salts of sulphuric acid monoesters of higher molecular alcohols or their polyglycol ethers, e.g. soluble salts of dodecyl alcohol sulphate, or of dodecyl alcohol polyglycol ether sulphate, or alkali metal salts of higher fatty acids (soaps), also non-ionic wash-active substances such as polyglycol ethers of higher fatty alcohols, also polyglycol ethers of higher molecular alkylated phenols as well as so-called amphoteric wash-active substances, e.g. reaction products of the alkali metal salts of low halogen fatty acids with polyalkylene polyamines containing lipophilic radicals such as with lauryl diethylenetriamine. In addition, the liquor can also contain the usual auxiliaries such as water soluble perborates, polyphosphates, carbonates, silicates, optical brighteners, plasticisers, salts having an acid reaction such as ammonium or zinc silicofiuoride, or certain organic acids such as oxalic acid, also finishers, e.g. those based on synthetic resins, or starch.

Primarily organic fibre material chiefly that of natural origin such as that containing cellulose, e.g. cotton, or containing polypeptide, e.g. wool or silk, or fibre material of synthetic origin such as that based on polyamide, polyacrylonitrile or polyester, or mixtures of the fibres mentioned above, can be sterilised with such washing or rinsing liquors containing active substance.

In concentrations of about l-200 p.p.m. (parts of active substance per diluent), the carbonic acid diesters usable according to the invention lend both to the liquor as well as to the articles washed therewith substantial and long-lasting freedom from germs of the staphylococci and coli forms, and this is maintained even after exposure of the active substance or of the goods treated therewith. They difi'er from previously known compounds by their stability to light on the goods laundered therewith and by their great activity and breadth of action against Grampositive and Gram-negative micro-organisms.

The new carbonic acid esters are also effective against bacteria which cause perspiration odours so that they are suitable as deodorants for personal linen and for incorporation into cleaning agents such as soaps or shampoos, or as additives to other cosmetics.

In addition, the carbonic acid diesters can be incorporated direct into the material to be protected, e.g. into material having a synthetic resin basis such as polyamides and polyvinyl chloride, into paper treatment liquors, into printing thickeners made of starch or cellulose derivatives, into lacquers and paints which contain, e.g. casein, into cellulose, into viscose spinning masses, paper, animal glues or oils, into permanent sizes based on polyvinyl alcohol. In addition they can also be added to preparations of inorganic or organic pigments for the painting and decorating industry, plasticisers etc. The carbonic acid diesters of Formula I can further be used in the form of their organic solutions, e.g. as sprays, in dry cleaning additives, or for the impregnation of wood. For this purpose, organic solvents, preferably non-water miscible solvents, particularly petroleum fractions, also however, water miscible solvents such as low alcohols, e.g. methanol or ethanol or ethylene glycol monomethyl or monoethyl ether, can be used. The carbonic acid diesters of Formula I can be used in the form of their aqueous dispersions together with Wetting or dispersing agents, e.g. for the protection of substances which tend to rot, e.g. leather, paper etc.

Solutions or dispersions of active substance which can be used for the protection of these materials should have a content of active substance of at least 0.001 g./litre.

In all these forms the new carbonic acid diesters of general Formula I can be the sole active substances or they can be combined with other known antimicrobial, particularly anti-bacterial and/ or antimycotic active substances. They can be combined with, e.g. halogenated and/ or halogenoalkyl-substituted salicyclic acid alkylamides and alkyl anilides, halogenated and/ or halogenoalkylsubstituted diphenyl ureas, optionally halogenated benzoxazolones, polychlorohydroxydiphenyl methanes, halogen-hydroxy-diphenyl sulphides, halogenated hydroxydiphenyl ethers, bactericidal Z-imino-imidazolidines or bactericidal quaternary compounds, dithiocarbamic acid derivatives or with tetramethyl thiuram disulphide. A broadening of the range of action and/or synergism occurs in some of the combinations mentioned of the carbonic acid diesters usable according to the invention with other antimicrobial active substances.

EXAMPLE 3 To a detergent composition liquefiable at high temperatures and compsed of Parts Sodium soap based on lauric, myristic and palmitic there are added at 85 to 90 Part 1-(3-chlorophenyl) 3 (4"-ch1orophenyl)-pyrazoline (optical brightener) 02 O-[2-(2",4"-dichlorophenoxy) 5 chlorophenyl]- O-(4'-n-octylpheny1) carbonate 1.0

The components are thoroughly mixed and then dried in the spray tower. A spreadable bactericidal detergent is obtained.

EXAMPLE 4 200 parts of soap powder, consisting of Percent Mixture of the sodium salt of tallow fatty acid and sodium salt of coconut oil fatty acid (weight ratio 70:30) 88.0 Almond oil 2.0 Perfume 1.0 Titanium dioxide 0.2 Glycerol 0.5 Tetrasodium salt of ethylene diamine tetraacetic acid 1-(3'-chlorophenyl) 3 (4"-ch1orophenyl)-pyrazoline (optical brightener) 0.05 O-[2-(2",4-dichlorophenoxy) 5 chlorophenyl1- O-(4' methoxyphenyl) carbonate 2.0 Water 6.2

together with 400 parts of water are worked at into a homogeneous mass and then dried at 70 to 80 in vacuo. A brightened bactericidal soap material material is obtained which can be formed into pieces or ground into a powder.

EXAMPLE 5 992 parts of a heavy-duty non-soap synthetic detergent consisting of Tetrasodium salt of ethylene diamine tetraacetic acid 3 Sodium sulfate 344 are mixed with 1000 parts of water to form a homogeneous slurry. To this mixture are added 1 part of 4,4'-bis [4",6-diphenylamino-l",3",5"-triazinyl (2")-amino]- stilbene-2,2-disulfonic acid (optical brightener) and 10 parts of O- [2- (4"-ch1orophenoxy) -5-chlorophenyl] -O- (4- n-nonylphenyl) carbonate, the whole is mixed well, then dried in the spray tower and ground into a powder. A bactericidal synthetic detergent powder is thus obtained.

We claim:

1. A process for the sterilisation of laundered goods and for the protection of laundered goods from attack by bacteria, comprising treating the goods to be laundered with a washing liquor which consists essentially of a detergent selected from the group consisting of anionic, nonionic and amphoteric detergents, and an antibacterially effective amount of diphenyl carbonate selected from the group consisting of compounds of the formula each of R and R represents hydrogen or halogen of an atomic number of at most 35,

the benzene ring B is unsubstituted; or monoto trisubstituted by members selected from the group consisting of halogen of an atomic number of at most 35, lower alkyl, and trifiuoromethyl, with the proviso that ring B may have no more than two trifluoromethyl groups attached thereto, and

the benzene ring is unsubstituted; monoto pentasubstituted by halogen of an atomic number of at most 35; or monoto tri-substituted by members selected from the group consisting of halogen of an atomic number of at most 35, alkyl having from 1 to 9 carbon atoms, alkoxy having from 1 to 9 carbon atoms, trifluoromethyl, phenyl, and halogenated phenyl, with the proviso that ring C may have no more than two trifluoromethyl groups, no more than one phenyl and no more than one halogenated phenyl group attached thereto.

2. A washing agent consisting essentially of a detergent selected from the group consisting of anionic, nonionic and amphoteric detergents and an antibacterially effective amount of diphenyl carbonate as defined in claim 1.

3. A washing agent consisting essentially of a detergent selected from the group consisting of anionic, nonionic and amphoteric detergents and an antibacterially effective amount of O-[2-(4"-chlorophenoxy)-5-chlorophenyl] -O-(4'-n-nonylphenyl] carbonate.

4. A washing agent consisting essentially of a detergent -selected from the group consisting of anionic, nonionic and amphoteric detergents and an antibacterially effective amount of O-[2-(2,4"-dichlorophenoxy)-5- chlorophenyl]-O-(4'-noctylphenyl) carbonate.

5. A washing agent consisting essentially of a detergent selected from the group consisting of anionic, nonionic and amphoteric detergents and an antibacterially effective amount of O-[2-(2,4-dichlorophenoxy)-5- chlorophenyl]-O- (4'-methoxyphenyl) carbonate.

References Cited UNITED STATES PATENTS 3,134,802 5/1964 Gaertner et a1. 260-463 FOREIGN PATENTS 659,636 8/ 1965 Belgium. 1,024,022 3/ 1966 Great Britain.

LEON D. ROSDOL, Primary Examiner P. E. WILLIS, Assistant Examiner US. Cl. X.R. 

